JP2005118714A - Esterification reaction catalyst - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a highly-active esterification reaction catalyst highly effective by use of a small amount, which scarcely colors and causes no bad influence on physical properties even if the catalyst remains. <P>SOLUTION: The catalyst is used for the esterification reaction (a) of an organic acid (b) selected from organometallic compounds represented by general formulae (1)-(3) and alcohol (c), wherein L represents a monovalent organic acid group represented by a halogen atom, R<SP>1</SP>-, R<SP>1</SP>O-, R<SP>1</SP>S-, R<SP>1</SP>OCO-, R<SP>1</SP>COO- and R<SP>1</SP>NHCO-; J<SP>1</SP>represents a monovalent organic acid group represented by R<SP>2</SP>OCO- and R<SP>2</SP>COO-; J<SP>2</SP>represents a divalent organic acid group represented by -OR<SP>3</SP>-OCO-, -OR<SP>3</SP>-COO-, -OCOR<SP>3</SP>-OCO-, -OCOR<SP>3</SP>-COO- and -OOCR<SP>3</SP>-COO-; n, p, q and r pieces of L may be the same or different; n, q and r are 2 or 3; p is 1 or 2; and M represents a titanium atom or a zirconium atom. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a catalyst for esterification reaction. More specifically, the present invention relates to an esterification reaction catalyst that is highly active and effective when used in a small amount, and that is less colored and does not adversely affect physical properties even when the catalyst remains.

Conventionally, as the esterification reaction catalyst, paratoluenesulfonic acid or sulfuric acid catalyst has been used, but the amount used was as large as 0.5% to 5%. If these catalysts remain, adversely affect the physical properties of the ester, such as poor thermal stability and coloring, and a catalyst removal step such as neutralizing with an aqueous alkali solution and filtering the generated neutralized salt is essential. there were.
In addition to the above catalysts, alkyl titanates such as tetraisopropyl titanate, tetrabutyl titanate, tetra-2-ethylhexyl titanate, and alkyl titaniums such as tetraisopropoxy titanium, tetrabutoxy titanium, tetra-2-ethylhexyl alkoxy titanium, etc. are also known. However, there is a problem that the ester compound that is deactivated due to water generated during the reaction causes a haze or coloration. (For example, Patent Document 1)
As a method not remaining in the ester compound, a method using a solid acid catalyst such as an ion exchange resin has been proposed. (For example, Non-Patent Document 1)
JP-A-3-31239 Catal Lett Vol. 78, No1 / 4; 185-188 (2002)

However, when a solid acid catalyst such as an ion exchange resin is used, the esterification reaction takes a long time, and when used in a large amount, there is a problem that it partially dissolves in the ester compound and precipitates during storage. Further, the use of these solid acid catalysts does not solve the problem of coloring.
That is, an object of the present invention is to provide a catalyst for an esterification reaction that is highly active and effective when used in a small amount, and that is less colored and does not adversely affect physical properties even if the catalyst remains.

As a result of intensive studies to achieve the above object, the present inventors have found that a catalyst for an organometallic compound having a specific structure exhibits an activity equivalent to that of a conventional catalyst in a small amount and is less colored. Reached.
That is, the present invention is an esterification reaction of an organic acid (b) and an alcohol (c), which is one or more selected from organic metal compounds represented by the following general formulas (1) to (3) Catalyst (a); and an ester production method in which an acid (b) and an alcohol (c) are reacted in the presence of the catalyst.
General formula

Wherein, L is a halogen ^{atom, R 1 -, R 1 O-} , R 1 S-, R 1 OCO-, R 1 COO-, R 1 NHCO-, in the monovalent organic group represented (however, R ¹ represents a monovalent hydrocarbon group having 1 to 30 carbon atoms in which the hydrogen atom may be substituted with a halogen atom; J ¹ represents a monovalent group represented by R ² OCO— or R ² COO—. Wherein R ² is a monovalent hydrocarbon group having 1 to 30 carbon atoms in which the hydrogen atom may be substituted with halogen, and may be the same as R ¹ ; and J ² is —OR ^{3 -OCO -, - OR 3 -COO} -, - OCOR 3 -OCO -, - OCOR 3 -COO -, - OOCR 3 -COO- a divalent organic group represented by (wherein, R ³ is the hydrogen atom Represents a divalent hydrocarbon group having 1 to 30 carbon atoms which may be substituted with halogen; and n, p, q and r L are the same. May be different. n, q, and r are 2 or 3, and p is 1 or 2. M represents a titanium atom or a zirconium atom. ]

The esterification reaction catalyst of the present invention has the following effects.
(1) The catalytic activity is extremely high, and a catalytic effect can be obtained by using a small amount.
(2) Little coloration, and even if the catalyst remains, the physical properties of the ester are not adversely affected.
(3) Since the catalyst removal step is unnecessary, the esterification step is simplified.

The esterification reaction catalyst of the present invention is at least one selected from organometallic compounds represented by the above general formulas (1) to (3) containing a titanium atom or a zirconium atom. Preferably, it is an organometallic compound represented by the general formula (1).
In the general formulas (1) to (3), the halogen atom is fluorine, chlorine, bromine or iodine. Preferably it is chlorine.

The monovalent hydrocarbon group represented by R ^{1 can} be a C 1-30 hydrocarbon group, and includes an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, and the like. Some hydrogen atoms may be substituted with halogen atoms (fluorine, chlorine, bromine, etc.). Although the number substituted with a halogen atom may be arbitrary, it is preferably 1 to 3.

Aliphatic hydrocarbon groups include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tertiary butyl, pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, octadecanyl, octyl, octadecyl, 2-monofluorononyl, trifluoro Examples include decyl, pentafluorotetradecyl, chlorooctyl, 1,1,1-trifluoromethyl and 1-monochloroethyl.
As the alicyclic hydrocarbon, a saturated alicyclic hydrocarbon and an unsaturated alicyclic hydrocarbon can be used.

  As the saturated alicyclic hydrocarbon, a saturated alicyclic hydrocarbon having 3 to 30 carbon atoms (preferably 3 to 20 and more preferably 3 to 15) is used. Specific examples include cyclopropyl, cyclobutyl, cyclopentyl, 2-methylcyclopropyl, cyclohexyl, cycloheptyl, 1-methylcyclopentyl, 1-methylcyclohexyl, dodecylcyclohexyl, 2,3,4-tripropylcyclohexyl, 2- Examples include methylcyclohexyl, 3,5-dimethylcyclohexyl, 2,4,6-trimethylcyclohexyl, 4,5-dichlorocyclodecyl and perfluorocyclohexyl.

  As the unsaturated alicyclic hydrocarbon, an unsaturated alicyclic hydrocarbon having 3 to 30 carbon atoms (preferably 3 to 20, more preferably 3 to 15) or the like is used. Specific examples include cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclododecenyl, cyclohexenyl, cycloheptenyl, 5-methylcyclotricosenyl, 2-methylcyclohexenyl, 3-methylcycloheptenyl, cyclooctenyl, 2,4,6-trichloro And cyclohexenyl and 2,3,4-trimethylcyclohexenyl.

As the aromatic hydrocarbon, an aromatic hydrocarbon having 6 to 30 carbon atoms (preferably 6 to 20 and more preferably 6 to 15) is used. Specific examples include phenyl, tolyl, xylyl, cumyl, mesyl, 1-ethylphenyl, 2-propylphenyl, 1-t-butylphenyl, 1,3,5-trimethylphenyl, 3-hexylphenyl, 3-octylphenyl. , 3-nonylphenyl, 3-decylphenyl, 5-dodecylphenyl, 3-phenylphenyl, 3-benzylphenyl, p-cumylphenyl, α-naphthyl, β-naphthyl, pentafluorophenyl, trifluoromethylphenyl, trifluoromethyl Naphthyl, 3-methyltetrafluorophenyl, p-trifluoromethyltetrafluorophenyl, 3,5-dimethyltrifluorophenyl, 2,4,5-trifluoromethylphenyl, 3,5-di [t-butyl] phenyl, 2,3,5-trimethylphenyl, indeni And azulenyl, fluorenyl, phenanthrenyl, anthracenyl, acenaphthylenyl, biphenylenyl, and perfluoro-3,4,5-tripropylphenyl.
Among the above R ^1, an aromatic hydrocarbon is preferable, and an aliphatic hydrocarbon is particularly preferable.

Examples of the monovalent organic group represented by R ¹ O— include an alkoxy group having 1 to 30 carbon atoms, an alkenyloxy group, a cycloalkoxy group, a cycloalkenyloxy group, and an aryloxy group, and a part of hydrogen The atom may be substituted with a halogen atom.
As an alkoxy group, a C1-C30 (preferably 1-20, more preferably 1-15) alkoxy group etc. are used, and methyloxy, ethyloxy, propyloxy, isopropyloxy, butyloxy, i-butyloxy, t -Butyloxy, pentyloxy, n-hexyloxy, 2-ethylhexyloxy, n-octadecyloxy, trifluoromethyloxy, dichloroethyloxy, perchloropropyloxy groups and the like.

As the alkenyloxy group, an alkenyloxy group having 2 to 30 carbon atoms (preferably 2 to 20, more preferably 2 to 10 carbon atoms) is used. 1,2-etheneoxy, 1,2-propenyloxy, 1,2 -Buteneoxy, 1,2-penteneoxy, 2-hexene-1-oxy, perchloroocteneoxy, 2-decanyloxy bromide group and the like.
As the cycloalkoxy group, a cycloalkoxy group having 3 to 30 carbon atoms (preferably 3 to 20, more preferably 3 to 15 carbon atoms) or the like is used. Cyclopropyloxy, cyclobutyloxy, cyclohexyloxy, 4-t-butyl Examples include cyclohexyloxy, cycloheptyloxy, cyclooctyloxy, 1,3-fluorocyclooctyloxy, perchlorocycloheptyloxy, methylcyclopropyloxy, trifluoroethylcyclohexyloxy, and the like.

As the cycloalkenyloxy group, a cycloalkenyloxy group having 3 to 30 carbon atoms (preferably 3 to 20, more preferably 3 to 15 carbon atoms) and the like are used. Cyclopropyleneoxy, cyclobuteneoxy, cyclopenteneoxy, cyclohexeneoxy and And perfluorocycloocteneoxy.
As the aryloxy group, an aryloxy group having 6 to 30 carbon atoms (preferably 6 to 20 and more preferably 6 to 15) is used, and phenoxy, cresyloxy, 2,3,4-trimethylphenoxy, 2,3 , 4-trinitrophenoxy, p-chlorophenoxy, pentachlorophenoxy, p-cyanophenoxy, 2,3-xylyloxy, nitrophenoxy, p-trifluoromethylphenoxy, pentafluorophenoxy and heptafluoronaphthyloxy and 3,4, 5,6-tetrapropylnaphthyloxy and the like.
Of the above R ¹ O—, an aryloxy group is preferred, and an alkoxy group is more preferred.

Examples of the monovalent organic group represented by R ¹ S— include those in which O in R ¹ O— is substituted with S, and preferred ones are the same as R ¹ O—.

Examples of the monovalent organic group represented by R ¹ OCO— include those in which a carbonyl group (CO) is added to the above R ¹ O. For example, an alkyloxycarbonyl group having 2 to 30 carbon atoms, an alkenyloxycarbonyl group, a cycloalkyloxycarbonyl group, a cycloalkenyloxycarbonyl group, an aryloxycarbonyl group, etc., and some of the hydrogen atoms are substituted with halogen atoms. May be.
Specific examples of these groups include those in which carbonyl (CO) is added to the above R ¹ O. The preferred ones are the same.

Examples of the monovalent organic group represented by R ¹ COO— include those in which a carboxy group (COO) is added to R ¹ . Examples thereof include an alkylcarboxy group having 2 to 30 carbon atoms, an alkenylcarboxy group, a cycloalkylcarboxy group, a cycloalkenylcarboxy group, and an arylcarboxy group, and some of the hydrogen atoms may be substituted with a halogen atom. Specific examples of these groups include those in which a carboxy group (COO) is added to R ¹ . The preferred ones are the same.

Examples of the monovalent organic group represented by R ¹ NHCO— include those in which an alkylaminocarbonyl group (NHCO) is added to R ¹ . For example, an alkylaminocarbonyl group having 2 to 30 carbon atoms, an alkenylaminocarbonyl group, a cycloalkylaminocarbonyl group, a cycloalkenylaminocarbonyl group, an arylaminocarbonyl group, etc., and some of the hydrogen atoms are substituted with halogen atoms. It may be. Specific examples of these groups include those in which an alkylaminocarbonyl group (NHCO) is added to R ¹ . The preferred ones are the same.

Examples of the monovalent organic group represented by R ¹ CONH— include those in which a carbonylamino group (CONH) is added to R ¹ . Examples thereof include alkylcarbonylamino, alkenylcarbonylamino, cycloalkylcarbonylamino, cycloalkenylcarbonylamino, arylcarbonylamino and the like, and some of the hydrogen atoms may be substituted with a halogen atom, a cyano group, or a nitro group. Specific examples of these groups include those in which a carbonylamino group (CONH) is added to R ¹ . The preferred ones are the same.
Of the above L, R ¹ S— is preferred, and R ¹ O— and R ¹ COO— are particularly preferred. These may be the same or different.

J ¹ is a monovalent organic group represented by R ² OCO— or R ² COO—. Here, R ² is a monovalent saturated hydrocarbon group or unsaturated hydrocarbon group having 1 to 30 carbon atoms in which the hydrogen atom may be substituted with a halogen atom. These may be independently substituted.

  Examples of the monovalent saturated hydrocarbon group having 1 to 30 carbon atoms and the substituted group thereof include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tertiary butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, Undecyl, dodecyl, tridecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, icosyl, heicosyl, docosyl, tricosyl, tetracosyl, pentacosyl, hexacosyl, heptacosyl, octacosyl, nonacosyl, triacontyl, methyl fluoride, ethyl fluoride, methyl chloride, chloride Examples include ethyl, propyl bromide, cyclohexenyl, cyclododecyl, 2-propylcyclohexenyl and the like.

  Examples of monovalent unsaturated hydrocarbon groups having 2 to 30 carbon atoms and substituted groups thereof include vinyl, propenyl, isopropenyl, butenyl, isobutenyl, tertiary butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonyl, decenyl, Undecenyl, tridecenyl, tetradecenyl, pentadecenyl, hexadecenyl, octadecenyl, nonadecenyl, icocenyl, henicosenyl, dococenyl, tricocenyl, pentacosenyl, hexacocenyl, heptacocenyl, octacocenyl, nonacosenyl, cyclofluoroenyl, cyclopropenyl, cyclopropenyl, hex , 2,3-trichloro-4-methylcyclohexyl) dodecenyl and the like.

Of these R ² , preferred are hexyl, hexacosyl, octacosyl, triacontyl, octenyl, decenyl, dodecenyl, tetradecenyl, hexadecenyl, octadecenyl, icocenyl, dococenyl, tetracocenyl, hexacocenyl, octacocenyl, triaconcenyl, and more preferred. Icosyl, docosyl and tetracosyl, particularly preferred is dodecyl, and most preferred are tetradecyl, hexadecyl and octadecyl.

Examples of the organic group represented by J ¹ in the general formula (1) include hexyloxycarbonyl, dodecyloxycarbonyl, tetradecyloxycarbonyl, hexadecyloxycarbonyl, octadecyloxycarbonyl, icosyloxycarbonyl, docosyloxycarbonyl. , Oxycarbonyls such as tetracosyloxycarbonyl, hexacosyloxycarbonyl, octacosyloxycarbonyl, hexacosenyloxycarbonyl, octacocenyloxycarbonyl, triaconenyloxycarbonyl; decanoic acid, dodecanoic acid, tetradecanoic acid , Hexadecanoic acid, octadecanoic acid, isaconic acid, docosanoic acid, tetracosanoic acid, hexacosanoic acid, octacosanoic acid, hexacocenyl carboxylic acid, octacocenyl carboxylic acid, triaconcenyl Carbonyl group derived from carboxylic acid.

Preferred among these J ¹ are derived from decanoic acid, dodecanoic acid, icosanoic acid, docosanoic acid, tetracosanoic acid, hexacosanoic acid, octacosanoic acid, hexacosenyl carboxylic acid, octacocenyl carboxylic acid, triaconenyl carboxylic acid. More preferred are carbonyl groups derived from dodecyloxycarbonyl and dodecanoic acid, icosanoic acid, docosanoic acid and tetracosanoic acid, and particularly preferred are derived from hexadecyloxycarbonyl and dodecanoic acid. A carbonyl group, most preferably tetradecyloxycarbonyl, octadecyloxycarbonyl, and a carbonyl group derived from tetradecanoic acid, hexadecanoic acid, and octadecanoic acid.

J ² is, -OCOR ³ OCO -, - OOCR a divalent organic group represented by ³ COO-. Here, R ³ is a C 1-30 divalent saturated hydrocarbon group or unsaturated hydrocarbon group in which the hydrogen atom may be substituted with a halogen atom. These may be independently substituted.

  Examples of the divalent saturated hydrocarbon group having 1 to 30 carbon atoms and the substituted group thereof include methylene, ethylene, propylene, isopropylene, butylene, isobutylene, t-butylene, pentylene, hexylene, octylene, nonylene, decylene, Undecylene, dodecylene, tridecylene, tetradecylene, hexadecylene, heptadecylene, octadecylene, nonadecylene, icosylene, henicosylene, docosylene, tricosylene, tetracosylene, pentacosylene, hexacosylene, heptacosylene, nonacosylene chloride, triaconethylene chloride, methylene fluoride, methylene fluoride Examples include methylene, ethylene chloride, propylene bromide, cyclohexalene, cyclododesalene, and 2-propylcyclohexylene group.

  Examples of the monovalent unsaturated hydrocarbon group having 2 to 30 carbon atoms and the substituted group thereof include vinylene, propenylene, isopropenylene, butenylene, isobutenylene, t-butenylene, pentenylene, hexenylene, octenylene, nonnylene, decenylene, Undecenylene, dodecenylene, tetradecenylene, pentadecenylene, hexadecenylene, heptadecenylene, octadecenylene, nonadecenylene, icosenylene, docosenylene, tricosenylene, tetracosenylene, pentacosenylene, hexacocenylene, heptacenylene, protacenylene, Pentenylene and 1- (1,2,3-trichloro-4-methylcyclohexyl) dodeceni Down group, and the like.

Among these R ³ , preferred are methylene, octylene, nonylene, and decylene groups, and more preferred are methylene fluoride, ethylene fluoride, methylene chloride, ethylene chloride, and propylene bromide groups, and particularly preferred. Butylene, pentylene and hexylene groups, and most preferred are ethylene and propylene groups.

Of J ² represented by the general formulas (2) and (3), preferred are methylenedioxycarbonyl, heptylenedioxycarbonyl, octylenedioxycarbonyl, nonylenedioxycarbonyl, decylenedioxycarbonyl group and heptylenedi. Carbonyl groups derived from carboxylic acids, octylene dicarboxylic acids, nonylene dicarboxylic acids, and decylene dicarboxylic acids, more preferred are fluorinated methylene dicarboxylic acids, fluorinated ethylene dicarboxylic acids, methylene chloride dicarboxylic acids, and ethylene dicarboxylic chlorides. Acid, carbonyl group derived from propylene dicarboxylic acid bromide, particularly preferred are butylene dioxycarbonyl, pentylene dioxycarbonyl, hexylene dioxycarbonyl group and butylene dicarboxylic acid, pentylene dicarboxylic acid A carbonyl group derived from the F-xylylene carboxylic acid, the most preferred are ethylene oxycarbonyl, propylene dioxy group and ethylene dicarboxylic acid, a carbonyl group derived from propylene dicarboxylic acids.
n, q, and r are 2 or 3, preferably 3. The n, q, and r L may be the same or different. p is 1 or 2, preferably 2. The n, q, and r L may be the same or different.

  As a manufacturing method of the catalyst for esterification reaction of this invention, it can manufacture by a well-known general method. For example, the methods described in detail in New Experimental Chemistry Course 12 (Organic Metal Chemistry) [Maruzen Publishing], Experimental Science Course 4th Edition 17 (Inorganic Complexes, Chelate Complexes) [Maruzen Publishing] can be mentioned. Specifically, for example, the following methods (1) to (3) may be mentioned, and the method (3) is preferred.

(1) In the case of producing a metal catalyst containing a monovalent organic group J ¹ or a divalent organic group J ² in the general formula (1), a halogen compound (d) containing titanium or zirconium as a raw material containing a metal [TiCl ₄ , ZrCl ₄ etc.] or an alkoxide compound (e) is used.
First, R ¹ OH, R ¹ OCOH, R ¹ COOH, R ¹ NHCOH, and R ¹ CONH ₂ , which are compounds containing R ¹ corresponding to L, are reacted with the halogen compound (d) or the alkoxide compound (e). Let Next, this reaction product is R ² OH, R ² OCOH, R ² COOH, R ² NHCOH, R ² CONH ₂ and R ³ which are compounds containing R ² and R ³ corresponding to J ¹ or J ^2. The metal catalyst of the present invention is obtained by reacting with a Grignard reagent (f) such as OH, R ³ OCOH, R ³ COOH, R ³ NHCOH, R ³ CONH ₂ or R ² MgBr.

(2) Titanium chloride or zirconium chloride is dissolved or dispersed in an appropriate solvent (xylene, toluene, ethyl acetate, chloroform, etc.) as necessary, and becomes an organic compound (R that is a compound containing the above R ^{1). 1} OH, R ¹ OCOH, R ¹ COOH, R ¹ NHCOH, R ¹ CONH ₂ ; R ² OH, R ² OCOH, R ² COOH, R ² NHCOH, R ² which is a compound containing the above R ² and R ³ CONH ₂ and R ³ OH, R ³ OCOH, R ³ COOH, R ³ NHCOH, R ³ CONH ₂ ) are added dropwise at 20 to 100 ° C. and reacted.
(3) Titanium tetrachloride, titanium alkoxide (eg, methoxide, ethoxide, etc.), zirconium chloride, zirconium alkoxide (eg, methoxide, ethoxide, etc.) are added dropwise at 20 ° C. to 100 ° C. to the acid that is a reactant used for esterification. It is obtained by removing the generated hydrochloric acid or alcohol under reduced pressure.

  Formation of the compound can be confirmed by infrared absorption spectroscopy or elemental analysis. For example, in infrared absorption spectroscopy, the stretch absorption peak position (1700-1750 cm-1) of the carbonyl (C = O) of the acid before the reaction becomes the peak position (1550-1600 cm-1) of the carbonyl ion after the reaction. To confirm the product. Moreover, reaction yield can be calculated | required by each peak ratio.

Examples of the esterification reaction catalyst (a) obtained by the above production method include the following.
As a catalyst having titanium as a central metal, trimethyldecanoic acid titanate, di (cyclohexyl) -di (oxydecanoic acid) titanate, phthalic acid-tri (fluorinated methoxy) titanate, isopropoxy-trihexanoic acid titanate, tetradecanoic acid titanate, Tetradodecanoic acid titanate, tetratetradecanoic acid titanate, tetrahexadecanoic acid titanate, tetraoctadecanoic acid titanate, di (tetradecanoic acid) -di (hexadecanoic acid) titanate, di (tetradecanoic acid) octadecanoic acid-titanium isopropoxide, triisopropoxy- Examples include dodecanoic acid titanate, methyl-hexanoic acid-dioctylalkoxy titanate, and dioctadecanoic acid-ethylene dicarboxylic acid titanate.

  Zirconium-based metal catalysts include trimethyldecanoic acid zirconate, di (cyclohexyl) -di (oxydecanoic acid) zirconate, phthalic acid-tri (fluorinated methoxy) zirconate, isopropoxy-trihexanoic acid zirconate, tetradecanoic acid zirconate. , Tetradodecanoic acid zirconate, tetratetradecanoic acid zirconate, tetrahexadecanoic acid zirconate, tetraoctadecanoic acid zirconate, di (tetradecanoic acid) -di (hexadecanoic acid) zirconate, di (tetradecanoic acid) octadecanoic acid-zirconium isopropoxide, triisopropoxy -Dodecanoic acid zirconate, methyl-hexanoic acid-dioctylalkoxy zirconate, dioctadecanoic acid-ethylene dicarboxylic acid zirconate and the like.

Among these catalysts for esterification reaction, organic compounds of titanium and zirconium having R ¹ O- (alkoxy group), R ¹ OCO- (alkyloxycarbonyl group), and R ¹ COO- (alkylcarboxy group) as ligands. Metal compounds are preferred. More preferred are organometallic compounds of titanium and zirconium having alkoxy, alkyloxycarbonyl and alkylcarboxy groups as ligands, and particularly preferred are organometallic compounds of titanium having alkoxy and alkylcarboxy groups as ligands. .

The ligand of the metal catalyst of the present invention can be arbitrarily selected from the groups listed in the above specific examples, but particularly when L, J ¹ and J ² are alkylcarboxy groups derived from carboxylic acid, esterification reaction The component derived from the carboxylic acid serving as the substrate (alkylcarboxy group) is preferably the same group. That is, for example, in the case of esterification reaction of stearic acid and 2-ethylhexyl alcohol, it is preferable to use stearic acid as a ligand from the viewpoint of compatibility between the catalyst and the reaction substrate.
In this way, when the ligand and the carboxylic acid component (alkylcarboxy group) that is the substrate of the reaction are the same, the catalyst of the present invention is produced in carboxylic acid, and the hydroxyl group-containing compound or the like can be produced without isolation. In addition, the dehydration condensation reaction can be performed, which is also efficient.

  The esterification reaction catalyst (a) of the present invention may be used alone or in combination of two or more. The amount of the esterification reaction catalyst used in the present invention is preferably 0.001 to 1 part by weight, more preferably 0.001 to 0.5 part by weight, per 100 parts by weight of the organic acid component in the production of the ester. Further, it may be used in combination with other known catalysts such as sulfuric acid, paratoluenesulfonic acid, titanium isopropoxide, titanium isobutoxide and the like well known in the esterification technology. The blending ratio when the other catalyst is used in combination with the ester reaction catalyst of the present invention is preferably 1: 1 to 1: 0.01 of the present catalyst: other catalyst, more preferably 1: 0.5 to weight ratio. 1: 0.05.

  The ester reaction performed using the esterification reaction catalyst of the present invention is a reaction between a known organic acid (b) and alcohol (c). These (b) and (c) can be used alone or in combination of two or more. In addition, when an acid group and a hydroxyl group exist in the same molecule as in hydroxycarboxylic acid and cyclize by esterification, it is regarded as esterification of the present invention.

As the organic acid (a) that can be used in the present invention, known organic acids conventionally used for ester production can be used.
Examples of such organic acids include carboxylic acids, phosphoric acids, and anhydrides thereof, and examples include the following (i) to (xiii). Of these, carboxylic acids are preferred.
(i) an aliphatic monocarboxylic acid having 1 to 30 or more carbon atoms (excluding carbon in the COOH group, the same shall apply hereinafter);
Saturated aliphatic monocarboxylic acids such as acetic acid, propionic acid, octylic acid and stearic acid; unsaturated aliphatic monocarboxylic acids such as (meth) acrylic acid and lauric acid;
(ii) an aliphatic polyvalent (preferably 2 to 8 valent) carboxylic acid having 1 to 30 or more carbon atoms;
Saturated aliphatic polyvalent carboxylic acids such as succinic acid, adipic acid, azelaic acid, sebacic acid; unsaturated aliphatic polyvalent carboxylic acids such as maleic acid, fumaric acid, itaconic acid, citraconic acid, glutaconic acid;
(iii) an aromatic monocarboxylic acid having 6 to 30 or more carbon atoms;
Benzoic acid, toluic acid, quinolinecarboxylic acid, p-chlorobenzoic acid and the like;

(iv) an aromatic polyvalent (preferably 2 to 8 valent) carboxylic acid having 6 to 30 or more carbon atoms;
Isophthalic acid, terephthalic acid, naphthalenedicarboxylic acid, diphenyldicarboxylic acid, etc .;
(v) an alicyclic monocarboxylic acid having 4 to 30 carbon atoms;
Cyclopropanecarboxylic acid, cyclobutanecarboxylic acid, etc .;
(vi) an araliphatic carboxylic acid having 7 to 15 or more carbon atoms;
2-phenylethanoic acid, monobenzylacetic acid, 1,2-diphenylhexanoic acid and the like;
(vii) anhydrides of (i) to (vi);
Maleic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, tetrabromophthalic anhydride, hexabromophthalic anhydride, hymic anhydride, het anhydride, etc .;

(viii) an aliphatic phosphoric acid, phosphorous acid, phosphonic acid having 1 to 30 or more carbon atoms;
Aliphatic phosphoric acid such as methyl phosphoric acid, ethyl phosphoric acid, dimethyl phosphoric acid, diethyl phosphoric acid, methyl ethyl phosphoric acid, dibutyl phosphoric acid, dihexyl phosphoric acid, di (2-ethylhexyl) phosphoric acid; methyl phosphorous acid, ethyl phosphorous acid The corresponding aliphatic phosphorous acid such as methylphosphonic acid, ethylphosphonic acid and the like corresponding to the above;
(ix) Aromatic phosphoric acid, phosphorous acid, phosphonic acid having 6 to 30 or more carbon atoms;
Phenyl phosphoric acid, pyridyl phosphoric acid, p-cresyl phosphoric acid di, diphenyl phosphoric acid, etc .; phenylphosphorous acid, pyridyl phosphorous acid, etc. corresponding aromatic phosphorous acid; phenylphosphonic acid, pyridylphosphonic acid, etc. The corresponding aromatic phosphonic acid;
(x) (viii) anhydride of (ix);
Anhydrides of the above phosphoric acids such as methyl phosphoric acid, ethyl phosphoric acid, phenyl phosphoric acid;

Although it does not specifically limit as alcohol (c), For example, a low molecular alcohol, polyether polyol, polyester polyol, polymer polyol etc. are mentioned. A low molecular weight alcohol is preferred.
Low molecular alcohols include aliphatic saturated alcohols such as methanol, ethanol, butanol, octanol and stearyl alcohol, aliphatic unsaturated alcohols such as allyl alcohol, propenyl alcohol, propargyl alcohol and oleyl alcohol, and araliphatic alcohols such as benzyl alcohol. Monohydric alcohols such as ethylene glycol, propylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, 3-methylpentanediol, diethylene glycol, neo Divalent amines such as pentyl glycol, 1,4-bis (hydroxymethyl) cyclohexane, 1,4-bis (hydroxyethyl) benzene, 2,2-bis (4,4′-hydroxycyclohexyl) propane Lucol; Trivalent alcohol such as glycerin and trimethylolpropane; 4- to 8-valent alcohol such as pentaerythritol, diglycerin, α-methylglucoside, sorbitol, xylit, mannitol, dipentaerythritol, glucose, fructose, sucrose, etc. Is mentioned.

Examples of the polyether polyol also include an alkylene oxide adduct of a compound selected from the group consisting of water, the above alcohol, phenol, an amino group-containing compound, a carboxyl group-containing compound, a thiol group-containing compound, and a phosphoric acid compound.
The alkylene oxide preferably has 2 to 4 carbon atoms, more preferably ethylene oxide (EO) or propylene oxide (PO). The number of added moles is not limited, but is preferably 1 to 100 moles.
Examples of the phenol to which alkylene oxide is added include phenols such as phenol and cresol; polyhydric phenols such as pyrogallol, catechol, and hydroquinone; bisphenols such as bisphenol A, bisphenol F, and bisphenol S.

  Examples of the amino group-containing compound include amines, polyamines, amino alcohols and the like. Specifically, ammonia; monoamines such as alkylamines having 1 to 20 carbon atoms (such as butylamine) and aniline; aliphatic polyamines such as ethylenediamine, trimethylenediamine, hexamethylenediamine, and diethylenetriamine; piperazine, N-aminoethyl Heterocyclic polyamines such as piperazine; alicyclic polyamines such as dicyclohexylmethanediamine and isophoronediamine; phenylenediamine, tolylenediamine, diethyltolylenediamine, xylylenediamine, diphenylmethanediamine, diphenyletherdiamine, polyphenylmethanepolyamine, etc. Aromatic polyamines; alkanolamines such as monoethanolamine, diethanolamine, triethanolamine, triisopropanolamine; dicarboxylic acids and excess Polyamide polyamines obtained by condensation with polyamines; polyether polyamines; hydrazines (hydrazine, monoalkylhydrazine, etc.), dihydrazides (succinic acid dihydrazide, adipic acid dihydrazide, isophthalic acid dihydrazide, terephthalic acid dihydrazide, etc.), guanidines ( Butyl guanidine, 1-cyanoguanidine, etc.); dicyandiamide, etc .; and mixtures of two or more thereof.

Examples of the carboxyl group-containing compound include aliphatic monocarboxylic acids such as acetic acid and propionic acid; aromatic monocarboxylic acids such as benzoic acid; aliphatic polycarboxylic acids such as succinic acid and adipic acid; phthalic acid, terephthalic acid, trimellit Examples thereof include aromatic polycarboxylic acids such as acids; polycarboxylic acid polymers (functional group number: 2 to 100) such as (co) polymers of acrylic acid.
Examples of the polythiol compound of the thiol group-containing compound include divalent to octavalent polyvalent thiols. Specific examples include ethylenedithiol, propylenedithiol, 1,3-butylenedithiol, 1,4-butanedithiol, 1,6-hexanedithiol, 3-methylpentanedithiol, and the like.
Examples of phosphoric acid compounds include phosphoric acid, phosphorous acid, and phosphonic acid.

  Examples of the polyester polyol include ring opening of low-molecular polyols [the above dihydric alcohol, trimethylolpropane, glycerin and the like] and the polycarboxylic acids obtained by reacting the polycarboxylic acids and lactones [ε-caprolactam, etc.]. Examples thereof include a polyester polyol obtained by polymerization and a recovered polyester polyol obtained by glycol decomposition of a polyester molded product.

  Examples of the polymer polyol include those obtained by polymerizing and stably dispersing a vinyl monomer such as acrylonitrile or styrene in the presence of a radical initiator in at least one of the polyols exemplified above. The content of the vinyl polymer in the polymer polyol is usually 5 to 50% by mass, preferably 10 to 40% by mass.

  As the hydroxycarboxylic acid, a hydroxycarboxylic acid having 2 to 20 carbon atoms can be used, and hydroxyacetic acid, lactic acid, glyceric acid, tartronic acid, tartaric acid, malic acid, hydroxystearic acid, hardened castor oil fatty acid, tropic acid, benzylic acid , Anisic acid, salicylic acid, vanillic acid, protocatechuic acid and gallic acid.

The ratio of the organic acid to the alcohol is preferably 2: 1 to 1: 2, more preferably 1: 1 to 1: 1.5, as the ratio of acid to OH.
The ester according to the present invention can be produced by a method similar to the conventional method. For example, the reaction temperature is preferably 50 to 250 ° C, more preferably 100 to 230 ° C. The reaction time is preferably 5 to 15 hours. Removal of water generated by esterification may be performed under normal pressure or reduced pressure, but the reaction is initially performed under normal pressure, and the reaction is preferably performed from the middle of the reaction or finally under reduced pressure. The degree of vacuum is preferably 30 mPa or less. The progress of the reaction can be determined by measuring the acid value.
Also, during the reaction, if necessary, stabilizers (phosphate esters, etc.), fillers as regulators (silica, titanium oxide, etc.), colorants (carbon black, dyes, etc.), oxidation stabilizers (hydroquinone, etc.) Etc. may be used.
Hereinafter, the present invention will be further described, but the present invention is not limited thereto.
In the following, parts and% indicate parts by weight and% by weight, respectively.
Each organometallic compound was identified by elemental analysis.

The following organometallic compounds were produced in a glove box in a nitrogen gas atmosphere.
In 1 liter of Kolben, 1080 parts (4 mol) of hexadecanoic acid is weighed, heated to 65 ° C. and dissolved. Thereto, 284 parts (1 mol) of tetraisopropoxy titanate was added in small portions over 10 minutes with stirring, and the mixture was stirred at the same temperature for about 10 minutes. Next, the product was cooled to 30 ° C., and the isopropyl alcohol generated by removing the pressure to 10 mPa was removed to obtain the desired product. It was identified as tetrahexadecanoic acid titanate (A) which is an organometallic compound of the present invention by elemental analysis and IR. The yield was 98%.
Elemental analysis values [%, values in parentheses are calculated values]
C: 72.5 (72.6), H: 11.7 (11.7), O: 11.2 (11.3).

In Example 1, instead of 1080 parts (4 moles) of hexadecanoic acid, 484 parts (2 moles) of tetradecanoic acid and 596 parts (2 moles) of octadecanoic acid were used in the same manner as in Example 1 to obtain the desired product. By elemental analysis and IR, it was identified as di (tetradecanoic acid) -di (octadecanoic acid) titanate (B) which is an organometallic compound of the present invention. The yield was 97%.
Elemental analysis value C: 72.6 (72.6), H: 11.5 (11.7), O: 11.5 (11.4).

In Example 1, in place of 1080 parts (4 mol) of hexadecanoic acid, 270 parts (1 mol) of hexadecanoic acid and 596 parts (2 mol) of octadecanoic acid were used in the same manner as in Example 1 to obtain the desired product. By elemental analysis and IR, it was identified as di (hexadecanoic acid) -octadecanoic acid titanium isopropoxide (C), which is an organometallic compound of the present invention. The yield was 98%.
Elemental analysis value C: 71.4 (71.6), H: 11.7 (11.8), O: 11.5 (11.5).

In 1 liter of Kolben, 540 parts (2 mol) of hexadecanoic acid and 118 parts (1 mol) of ethylenedicarboxylic acid are weighed and heated to 40 ° C. Thereto, 189.67 parts (1 mol) of titanium chloride was added in portions over 10 minutes while stirring, and the mixture was stirred as it was for about 10 minutes. Next, the product was obtained by cooling to 30 ° C. and removing hydrochloric acid generated by reducing the pressure to 1 mPa. By elemental analysis and IR, it was identified as di (hexadecanoic acid) -ethylene dicarboxylic acid titanium salt (D) which is an organometallic compound of the present invention. The yield was 97%.
Elemental analysis value C: 65.1 (65.2), H: 10.0 (10.0), O: 18.1 (18.2).

The target product was obtained in the same manner as in Production Example 1 except that tetraisopropoxide titanium was changed to tetraisopropoxide zirconium. It was identified as tetrahexadecanoic acid zirconium salt (E) which is an organometallic compound of the present invention by elemental analysis and IR. The yield was 97%.
Elemental analysis value C: 67.0 (66.9), H: 11.3 (11.3), O: 11.0 (11.0).

<Comparative Catalyst Example 1> Commercially available sulfuric acid (F) was used.
<Comparative Catalyst Example 2> Commercially available tetraisopropoxy titanium (G) was used.

  Using the catalysts (A) to (E) of the organometallic compounds of the present invention of Examples 1 to 5 and the catalysts (F) and (G) of Comparative Examples 1 and 2, esterification is performed by the following method, The reaction time was determined.

540 parts of hexadecanoic acid (HD) and 0.13 part of tetrahexadecanoic acid titanate (A) obtained in Example 1 were added to 2 liters of Kolben, and the mixture was gradually heated to 150 ° C. with stirring while blowing nitrogen. 316 parts of dodecanol (Dnol) was added after the temperature in the system reached around 60 ° C. during the temperature elevation. Stirring was continued even after reaching 150 ° C., and the generated water was made open and discharged out of the system. The reaction rate obtained from the acid value reached 99.9% to obtain an ester compound. The time required for the reaction was about 8 hours.
Hereinafter, the time required for the reaction similarly refers to the time when the reaction rate has reached 99.9%.

  The acid component was 596 parts of octadecanoic acid (OD), the catalyst was 0.3 part of bis (tetradecanoic acid) -bis (octadecanoic acid) titanate (B) obtained in Example 2, and the hydroxyl group-containing compound component was 2-ethylhexanol ( Ehnol) An ester compound was obtained in the same manner as in Example 1 except that the amount was changed to 260 parts. The time required for the reaction was about 8 hours.

  An ester compound was obtained in the same manner as in Example 1, except that the catalyst was changed to 0.2 parts of di (hexadecanoic acid) -octadecanoic acid titanium isopropoxide (C) obtained in Example 3. The time required for the reaction was 9 hours.

  A mixture of 30 parts of maleic anhydride (aMA) and 150 parts of octadecanoic acid as an acid component, 0.1 part of bishexadecanoic acid-ethylenedicarboxylic acid titanium salt (D) obtained in Example 4, and alcohol as castor oil An ester compound was obtained in the same manner as in Example 1 except that EO 2.5 mol adduct (YEO 2.5) was changed to 840 parts. The time required for the reaction was 11 hours.

  Example except that the acid component is changed to 850 parts (YPO) of palm oil fatty acid, the catalyst is changed to 0.15 part of tetrahexadecanoic acid zirconium salt (E) obtained in Example 5, and the alcohol is changed to 200 parts of trimethylolpropane (TMP). In the same manner as in Example 1, an ester compound was obtained. The time required for the reaction was about 11 hours.

<Comparative Example 3>
An ester compound was obtained in the same manner as in Example 1 except that the catalyst was changed to 2.5 parts of sulfuric acid (F) in Comparative Catalyst Example 1. The time required for the reaction was about 9 hours.

<Comparative example 4>
An ester compound was obtained in the same manner as in Comparative Example 1 except that the amount of the catalyst was changed to 0.13 part. The time required for the reaction was 47 hours.

<Comparative Example 5>
An ester compound was obtained in the same manner as in Example 3 except that the catalyst was changed to 3 parts of tetraisopropoxytitanium (G) of Comparative Catalyst Example 2. The time required for the reaction was 16 hours.

<Comparative Example 6>
An ester compound was obtained in the same manner as in Comparative Example 3 except that the amount of catalyst was changed to 0.2 part. The time required for the reaction was 59 hours.

Table 1 shows the esterification catalyst, the organic acid component, the alcohol component, the time required for the reaction (hr), the Hazen color number, and the haze used in Examples 6 to 10 and Comparative Examples 3 to 6.
The measurement method was as follows.
[Acid Value] The acid value was based on JIS K6751.
[Haze] About 1 g or more (so that it slightly protrudes from the washer) is put in a washer having a thickness of 2 mm and an inner diameter of 1 cm. The ester cooled to room temperature (25 ° C.) was visually judged as hazy based on the following criteria.
Judgment criteria ○: Faint (transparent)
Δ: Blurred
[Coloring] Coloring was expressed using Hazen frequency.

The symbols in the above table are as follows.
As acid HD: Hexadecanoic acid OD: Octadecanoic acid aMA: Maleic anhydride YPO: As palm oil fatty acid alcohol Dnol: Dodecanol Ehnol: 2-ethylhexanol TMP: Trimethylolpropane YEO2.5: EO2.5 mol adduct catalyst of castor oil (A): Tetrahexadecanoic acid titanate (B): Di (tetradecanoic acid) -di (octadecanoic acid) titanate (C): Di (hexadecanoic acid) -octadecanoic acid titanium isopropoxide (D): Di (hexadecanoic acid) -Ethylenedicarboxylic acid titanium salt (E): Tetrahexadecanoic acid zirconium salt (F): Sulfuric acid (G): Tetraisopropoxytitanium

As is clear from Table 1, all the organometallic catalysts of Examples 6 to 10 of the present invention have the same reaction time until the end of esterification as that of the conventional sulfuric acid catalyst of Comparative Example 1, As shown, the conventional catalyst has low activity in a small amount, which is significantly different from the effect of the catalyst of the present invention.
Even in the case of a catalyst having the same titanium as the central metal, the conventional titanium-based catalyst such as tetraisopropoxide is low in activity as in Comparative Examples 3 and 4, and the same amount is added as shown in Comparative Example 4. Even in this case, it is shown that the coloring is intense.

It is useful as a catalyst for esterification reaction of an organic acid such as carboxylic acid, phosphoric acid or its anhydride with an alcohol.

Claims (6)

Catalyst for esterification reaction of organic acid (b) and alcohol (c) (a), which is at least one selected from organic metal compounds represented by the following general formulas (1) to (3) .
General formula

Wherein, L is a halogen ^{atom, R 1 -, R 1 O-} , R 1 S-, R 1 OCO-, R 1 COO-, R 1 NHCO-, in the monovalent organic group represented (however, R ¹ represents a monovalent hydrocarbon group having 1 to 30 carbon atoms in which the hydrogen atom may be substituted with a halogen atom; J ¹ represents a monovalent group represented by R ² OCO— or R ² COO—. Wherein R ² is a monovalent hydrocarbon group having 1 to 30 carbon atoms in which the hydrogen atom may be substituted with halogen, and may be the same as R ¹ ; and J ² is —OR ^{3 -OCO -, - OR 3 -COO} -, - OCOR 3 -OCO -, - OCOR 3 -COO -, - OOCR 3 -COO- a divalent organic group represented by (wherein, R ³ is the hydrogen atom Represents a divalent hydrocarbon group having 1 to 30 carbon atoms which may be substituted with halogen; and n, p, q and r L are the same. May be different. n, q, and r are 2 or 3, and p is 1 or 2. M represents a titanium atom or a zirconium atom. ] The catalyst for esterification reaction according to claim ^1, wherein L is R ¹ O- or R ¹ COO-. The catalyst for esterification reaction according to claim 1 or 2, wherein J ¹ is R ¹ COO-. The catalyst for esterification reaction according to claim 1 or 2, wherein the J ² is -OOCR ³ -COO-. The manufacturing method of ester which reacts organic acid (b) and alcohol (c) in presence of the catalyst (a) in any one of Claims 1-4. The ester compound obtained by the manufacturing method of Claim 5.